1- O-(Acylaminoacyl)-2,3,4,6-tetra- O-benzyl- D-glucopyranoses were prepared in high yields by two routes involving direct participation of imidazole in the ester linkage formation; namely, ( a) the accelerated active-ester method, and ( b) the imidazole-promoted dicyclohexylcarbodiimide condensation. The compounds were synthesized from 2,3,4,6-tetra- O-benzyl-α- D-glucopyranose and pentachlorophenyl esters of optically active benzyloxycarbonyl- and tert-butyloxycarbonyl-amino acids in method ( a) or benzyloxycarbonyl- and acetyl-amino acids in method ( b). By both methods, anomeric mixtures of D-glucosyl esters were obtained; they were resolved by column chromatography and the α and β anomers were fully characterized. The retention of configuration of the amino acid moiety was determined from optical rotations of acylamino acid methyl esters formed from D-glucosyl esters with methanolic sodium methoxide. With benzyloxycarbonyl and tert-butyloxycarbonyl protecting groups, a high degree of retention of optical activity was established in both methods-method ( a) being slightly superior.